Methods and compositions for doping silicon substrates with molecular monolayers

ABSTRACT

Compositions and methods for doping silicon substrates by treating the substrate with a diluted dopant solution comprising tetraethylene glycol dimethyl ether (tetraglyme) and a dopant-containing material and subsequently diffusing the dopant into the surface by rapid thermal annealing. Diethyl-1-propylphosphonate and allylboronic acid pinacol ester are preferred dopant-containing materials, and are preferably included in the diluted dopant solution in an amount ranging from about 1% to about 20%, with a dopant amount of 4% or less being more preferred.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 13/042,541 filed Mar. 8, 2011, and claims thepriority benefit of the provisional application U.S. Ser. No. 61/311,516filed Mar. 8, 2010 which are hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to methods for doping a Sisurface, and more particularly to methods for doping a Si surface bytreating the substrate with a dopant solution and subsequently diffusingthe dopant into the surface by rapid thermal annealing.

BACKGROUND OF THE INVENTION

Decreasing device size has been the main driving force for technologyadvancements in the semiconductor industry over the last severaldecades. For example, in front end of line (FEOL) applications insemiconductor processing, junction depths have been scaled continuouslytogether with the gate lengths in order to achieve faster transistorspeeds and higher packing densities. Typically, source/drain extensionjunction depths of about one third of the transistor gate length havebeen used for efficient electrostatics and acceptable leakage currents.With gate lengths fast approaching the sub-10 nm regimes, developmentwork is focused on reliably making sub-5 nm ultrashallow junctions(USJs) with low sheet resistivity to facilitate the future scaling oftransistors.

Most commonly, USJs are commercially fabricated by the combination ofion implantation and spike annealing. During the process, Si atoms aredisplaced by energetic dopant ions and a subsequent annealing step (e.g.spike, a high temperature anneal process of less than 1 s with fasttemperature ramp up/down capability) is used to activate the dopants bymoving them into the appropriate lattice positions and restoring thesubstrate's crystal quality. Unfortunately, point defects such as Siinterstitials and vacancies are also generated, which interact with thedopants to further broaden the junction profile—calledtransient-enhanced diffusion (TED), which limits the formation forsub-10 nm USJs by conventional technologies.

Significant research efforts have been made to develop new strategies tomanufacture <5 nm USJs which utilize heavier implantation dopant sources(molecular implantation, gas cluster ion beam, and plasma doping) toobtain shallower doping profiles, and advanced annealing techniques(flash and laser) to activate the implanted dopants without causingsignificant diffusion. However, problems relating to the effects ofadvanced doping and annealing techniques on junction uniformity,reliability and subsequent process integration continue to hamper theiruse in IC manufacturing.

One potential route for achieving the USJs, while maintaining controlleddoping of semiconductor materials with atomic accuracy, at such smallscales, takes advantage of the crystalline nature of silicon and itsrich, self-limiting surface reaction properties. This method relies onthe formation of self-assembled monolayers of dopant-containingmolecules on the surface of crystalline Si followed by the subsequentthermal diffusion of dopant atoms via rapid thermal annealing (RTA).

Ground-breaking work in this area has been performed by Professor AliJavey at Berkeley (Nature Materials, vol. 7, January 2008, pp 62-67;Nanoletters, 2009 Vol. 9, No 2, pp 725-730). Dr. Javey and his groupsuccessfully doped silicon wafers by treating the Si surfaces with adopant dissolved in mesitylene (the dopant being allylboronic acidpinacol ester for p-doped wafers, and diethyl-1-propylphosphonate forn-doped wafers), and subsequently annealing the material to diffuse thedopant atoms into the surface and achieve the n+/p USJs. Dr. Javey'sresults were confirmed by SIMS, and penetration depth for P-containingmixtures were observed to be ˜3-3.5 nm.

Problems remain to be solved with the Javey process though. For example,the mesitylene-containing treatment solutions used by Dr. Javey are notappropriate for commercial applications where high surface modificationreaction temperatures are employed and commercial-scale materialhandling considerations are important. Accordingly, a need remains forimprovements to Dr. Javey's method for doping silicon substrates. Thepresent invention addresses that need.

SUMMARY OF THE INVENTION

In one preferred embodiment of the present invention there is provided amethod for doping a Si surface comprising treating the substrate with adiluted dopant solution comprising tetraethylene glycol dimethyl ether(tetraglyme) and a dopant-containing material and subsequently diffusingthe dopant into the surface. Dithyl-1-propylphosphonate and allylboronicacid pinacol ester are preferred dopant-containing materials, and arepreferably included in the diluted dopant solution in an amount rangingfrom about 1% to about 20%, with a dopant amount of 4% or less beingmore preferred. A capping layer is preferably applied prior todiffusion, such as by depositing silicon oxide or silicon nitride. Adiffusion step is preferably accomplished by rapid thermal annealing.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart showing the penetration depth of phosphorus atoms orboron atoms into the silicon substrate after a capping and hightemperature annealing process.

FIG. 2 is a SIMS chart showing the result after multiple loadings ofdiethyl-1-propylphosphonate in a solvent solution.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For the purposes of promoting an understanding of the principles of theinvention, reference will now be made to certain embodiments andspecific language will be used to describe the same. It willnevertheless be understood that no limitation of the scope of theinvention is thereby intended, such alterations and furthermodifications of the illustrated embodiments being contemplated as wouldnormally occur to one skilled in the art to which the invention relates.

In one aspect of the present invention there is provided a method fordoping a Si surface by treating the substrate with a diluted dopantsolution comprising tetraethylene glycol dimethyl ether (tetraglyme) anda dopant-containing material and subsequently diffusing the dopant intothe surface.

In the preferred embodiments the Si surface is initially cleaned toremove oxides and provide an H-terminated silicon surface. The initialcleaning may be accomplished using dilute HF, for example. Additionalsteps may also be employed to protect the surface until thetetraglyme-dopant treatment, such as treating the surface with3-methyl-3-methoxybutanol.

In one preferred aspect of the present invention tetraethylene glycoldimethyl ether (tetraglyme) is used as a solvent to provide adopant-containing material to the cleaned Si substrate. The solventinteracts with the dopant molecules, carrying them to the siliconsurface and thereby allows control of the amount of dopant that isapplied to the surface.

The tetraglyme is preferably included in an amount appropriate to dilutethe dopant material to an amount less than 20% and preferably no morethan 4%. If no additional solvents are used the amount of tetraglyme maybe 80% or more, and preferably 96% or more. If additional solvents areused the amount of tetraglyme may be correspondingly less.

In another embodiment the solvent system comprises a solvent instead ofor in addition to tetraglyme. Preferred additional or alternativesolvents have individual flash points above 120° C., or provide asolvent system having a combined flash point above 120° C. Preferredadditional or alternative solvents also have a contact angle of 0° whenapplied to a Si surface, and are miscible with water. In otherembodiments the additional or alternative solvent has thosecharacteristics and is a polar solvent.

The secondary solvent that may replace or be used in addition totetraglyme may include one or more of the following: dimethylsulfoxide(DMSO), dimethylsulfone, N-methylpyrrolidone (NMP), 1 formyl piperidine,other gycol ethers such as triglyme or diglyme, isopar solvent blendssuch as Isopar M, alkanolamines such as ethanolamine, diethanolamine,triethanolamine, fatty acids such as linoleic acid, oleic acid,palmitoleic acid, and mixtures of fatty acids in such solvents assafflower oil, grape seed oil, poppyseed oil, sunflower oil, hemp oil,corn oil, wheat germ oil, cottonseed oil, soybean oil, walnut oil,sesame oil, rice bran oil, pistachio oil, peanut oil, canola oil,chicken fat, egg yolk, linseed oil, lard, olive oil, palm oil, cocoabutter, macadamia oil, butter, and coconut oil.

As to the dopant, diethyl-1-propylphosphonate and allylboronic acidpinacol ester are preferred dopant-containing materials. In someembodiments other dopants effective for producing n-doped or p-dopedsurfaces may be used in addition to or instead ofdiethyl-1-propylphosphonate and/or allylboronic acid pinacol ester. Forexample, arsenic or another Group V material may be used in addition toor in place of phosphorus, and galium or another Group III material maybe used in addition to or in place of boron.

In other embodiments the dopant comprises 5-5Dimethyl-1,3,2-dioxaphosphorinan-2-one. In another embodiment the dopantcomprises triphenylphosphate. In another embodiment the dopant comprisestrimethylphosphite. In another embodiment the dopant comprises diethylethylphosphonate. In another embodiment the dopant comprises dimethylmethylphosphonate. In another embodiment the dopant comprises diethyl(2-oxobutyl) phosphonate. In another embodiment the dopant comprisesdiethyl (hydroxymethyl)phosphonate. In another embodiment the dopantcomprises dimethyl (3-phenoxyacetonyl)phosphonate. In another embodimentthe dopant comprises bis(4-methoxyphenyl)phosphine. In anotherembodiment the dopant comprises bis(3,5-dimethylphenyl)phosphine. Inanother embodiment the dopant comprises diethyl(2-oxopropyl)phosphonate. In another embodiment the dopant comprisesdiethyl 1-phenylethyl phosphonate. In another embodiment the dopantcomprises diethyl 2-phenylethyl phosphonate. In another embodiment thedopant comprises diethyl cyclopropylmethyl phosphonate. In anotherembodiment the dopant comprises dimethyl (3-phenoxyacetonyl)phosphonate.In another embodiment the dopant comprises diethyl(2-methylallyl)phosphonate. In another embodiment the dopant comprisesone or more members selected from the group consisting of 5-5Dimethyl-1,3,2-dioxaphosphorinan-2-one, triphenylphosphate,trimethylphosphite, diethyl ethylphosphonate, dimethylmethylphosphonate, diethyl (2-oxobutyl) phosphonate, diethyl(hydroxymethyl)phosphonate, dimethyl (3-phenoxyacetonyl)phosphonate,bis(4-methoxyphenyl)phosphine, bis(3,5-dimethylphenyl)phosphine, diethyl(2-oxopropyl)phosphonate, diethyl 1-phenylethyl phosphonate, diethyl2-phenylethyl phosphonate, diethyl cyclopropylmethyl phosphonate,dimethyl (3-phenoxyacetonyl)phosphonate, diethyl(2-methylallyl)phosphonate, and Diethyl-1-propyl phosphonate.

The dopant material is preferably included in the diluted dopantsolution in an amount ranging from about 1% to about 20%, with a dopantamount of 1% to 10% being more preferred, and a doping amount of 4% orless being most preferred in testing to date.

A capping layer is preferably applied prior to diffusion, such as bydepositing silicon oxide or silicon nitride. In one embodiment a 50 nmthick capping layer is applied by plasma enhanced chemical vapordeposition (PECVD) prior to diffusion.

The dopant material is diffused into the Si surface by annealing afterthe deposition of a capping layer. Preferably, rapid thermal annealing(RTA) is used.

Reference will now be made to specific examples using the processesdescribed above. It is to be understood that the examples are providedto more completely describe preferred embodiments, and that nolimitation to the scope of the invention is intended thereby.

EXAMPLE 1 Solubility Testing

A variety of solvents were evaluated as potential replacements formesitylene in allylboronic acid pinacol ester:mesitylene anddiethylpropyl-phosphonate:mesitylene systems. The candidate solventsincluded: 1) Dimethylsulfoxide (DMSO); 2) N-methylpyrrolidone (NMP); 3)1-formyl piperidine (1-FP); 4) tetraglyme, (TG); and 5) Isopar M (IM).

Solubility was tested with diethyl 1-propylphoshonate 97% (n-typedopant) and allylboronic acid pinacol ester (p-type dopant). Solvent toadditive ratio (n or p type) material is 1:4. Solubility results areprovided below:

Solvent and Diethyl 1- Solubility observations after 12 hrs,propylphoshonate @ 23° C. DMSO Clear, stayed in sol'n NMP Clear, stayedin sol'n 1-FP Clear, stayed in sol'n TG Clear, stayed in sol'n IM Clear,stayed in sol'n

Solvent and Allyboronic Solubility observations after 12 hrs, acidpinacol ester @ 23° C. DMSO Slightly cloudy, stayed in sol'n NMPSlightly cloudy, stayed in sol'n 1-FP Clear, stayed in sol'n TG Clear,stayed in sol'n IM Clear, stayed in sol'n

All of the materials were soluble and stayed in solution. They werechecked after 12 hours, having been maintained at room temperature.

EXAMPLE 2 Contact Angle Testing

Contact angle testing was also conducted. Silicon substrates (n-dopedand p-doped prior to testing) were submerged in 0.5% HF(aq) for 2minutes at room temperature (23° C.) before testing contact angles. DIwater and mesitylene were used as references.

The observed contact angles on Si (100) n-type and p-type are reportedbelow:

Solvent and Diethyl 1- propylphoshonate Substrate Contact AngleMesitylene n-doped Si No reading = 0 p-doped Si No reading = 0 DMSOn-doped Si No reading = 0 p-doped Si Avg. = 22.57° NMP n-doped Si Noreading = 0 p-doped Si No reading = 0 1-Formyl Piperidine n-doped Si Noreading = 0 p-doped Si No reading = 0 Tetraglyme n-doped Si No reading =0 p-doped Si No reading = 0 Isopar M n-doped Si No reading = 0 p-dopedSi No reading = 0

Solvent and Allylboronic acid pinacol ester Substrate Contact AngleMesitylene n-doped Si No reading = 0 p-doped Si No reading = 0 DMSOn-doped Si No reading = 0 p-doped Si No reading = 0 NMP n-doped Si Noreading = 0 p-doped Si No reading = 0 1-FP n-doped Si No reading = 0p-doped Si No reading = 0 TG n-doped Si No reading = 0 p-doped Si Noreading = 0 IM n-doped Si No reading = 0 p-doped Si No reading = 0

Substrate Contact Angle DI water n-doped Si Avg. = 78.89° p-doped SiAvg. = 73.52°

The contact angle testing indicated that all of the tested solventsother than DMSO have no contact angle and therefore wet the surface ofthe substrate. Given the contact angle measurement for DMSO, it wasexcluded from further testing.

EXAMPLE 3 Phosphorus Doping

Diluted dopant solutions were used to dope a Si substrate. The followingglassware was used for the doping testing: 3 neck round bottom flask(500 mL), 2 distilling columns, stainless steel tube for N₂ inlet, 2thermometer adaptors, Y distillation adaptor, 4 tubes for columns andN₂, circulation bath, thermometer, heating mantel.

The following materials were used: N₂ (ultra high purity), EthyleneGlycol/water mixture (1:1), experimental solution (solutions used arelisted below), 3-methyoxy-3-methylbutanol, 0.5% HF solution, IPA, n-typeSi substrate, p-type Si substrate.

The test procedure was as follows:

-   1. Set up the glassware, reflux bath (ethylene glycol and DI 1:1),    place round bottom flask on heating mantel, cleave Si substrate into    small pieces about 1½ cm×1½ cm for testing. Both n- and p-type    substrates were processed at the same time.-   2. Prepare Solutions:    -   HF (0.5% in solution)    -   3-methoxy-3-methylbutanol    -   Experimental solution:        -   Solution #1—TG and diethyl 1-propylphonate 4:1 (v/v)—20 g            total in flask        -   Solution #2—1-FP and diethyl 1-propylphonate 4:1 (v/v)—20 g            total in flask        -   Solution #3—TG and allylboronic acid pinacol ester 4:1            (v/v)—20 g total in flask        -   Solution #4—1-FP and allylboronic acid pinacol ester 4:1            (v/v)—20 g total in flask-   3. Purge the round bottom flask containing the desired solution with    N₂, bubbling the N₂ though the fluid for an hour at room    temperature.-   4. Heat solution to 120° C. using the heating mantel, start the    cooling liquid flow (˜10° C.) through the condenser while heating    and continue its flow throughout the doping process.-   5. Once the solution is at 120° C., prepare substrates by processing    them in room temperature solutions of HF (2 min) and then    3-methoxy-3-methylbutanol (30 s).-   6. Immediately after step 5, place the treated substrates in a round    bottom flask containing heated dilute doping solution for 2.5 h at    120° C., and continue the N₂ bubbling.-   7. After 2.5 hours, cool the glassware apparatus and solution for 15    to 20 minutes, with the cooling water still running through the    condenser before removing the pieces.-   8. Rinse pieces in IPA after removing from the solution.-   9. Deposit silicon oxide or silicon nitride or other appropriate    capping material, such as plasma enhanced tetraethylorthosilicate    (PETEOS).-   10. Carry out a high temperature anneal process (1050° C. anneal),    and characterize by Secondary Ion Mass Spectrometry (SIMS).

SIMS is an analytical technique that detects very low concentrations ofdopants and impurities. It can provide elemental depth profiles over adepth range from a few angstroms to tens of microns. SIMS works bysputtering the sample surface with a beam of primary ions. Secondaryions formed during the sputtering are extracted and analyzed using amass spectrometer. These secondary ions can range from matrix levelsdown to sub-parts-per-million trace levels. This technique was used todetermine if phosphorus atoms (from diethyl 1-propylphosphonate) orboron atoms (from allylboronic acid pinacol ester) penetrated into thesilicon substrate after the capping and high temperature annealingprocesses. Results are shown in FIG. 1. The x-axis indicates the depthof penetration of each atom type that was monitored (and is indicated onthe graph's legend)

In the above example, one sample was created using mesitylene as thesolvent, and one was prepared using tetraglyme (TG) as the solvent. Thesamples were compared using SIMS to generate data for the comparison.The system using tetraglyme as the solvent provided phosphorus to thesurface and, after capping and annealing, allowed the phosphorus topenetrate the Si deeper than the phosphorus provided to the siliconsurface by the mesitylene solvent system.

Additional SIMS results after multiple loadings of diethyl1-propylphoshonate in the solution are provided in FIG. 2.

The results for the phosphorus doped samples indicate that doping depthcan be controlled by one or a combination of factors such as dopingconcentration, time, and temperature.

EXAMPLE 4 Representative Production Process

The doped surfaces of the present invention may be produced by thefollowing process:

1. Clean and dry a patterned Si wafer, preferably using DHF solution;

2. Clean immersion tank;

3. Rinse cleaned tank with tetraglyme or doping solution multiple timesuntil all the solution that was used for cleaning is purged;

4. Fill tank with doping solution to a level great enough to completelycover the wafers to be doped;

5. Heat the doping solution to the temperature required to create alayer of dopant on the silicon;

6. Completely immerse the wafers in the doping solution for timerequired to create a layer of dopant on the silicon;

7. Rinse wafers with appropriate solvent (for example, IPA or H₂O); and

8. Dry the wafers with N₂.

Subsequent to the above, the doped surfaces may be treated as follows:

1. Oxide deposition; and

2. Annealing to promote dopant diffusion.

Appropriate process steps for capping the doped surface (oxidedeposition) and for annealing to promote dopant diffusion may beaccomplished using methods known to persons skilled to the art.

While the compositions and methods of the present invention have beendescribed by reference to certain preferred embodiments, it will beapparent to those of skill in the art that variations may be applied tothe compositions and methods described herein without departing from theconcept and spirit of the invention. All such modifications apparent tothose skilled in the art are desired to be protected, and are deemed tobe within the scope of the invention as herein disclosed and claimed.

What is claimed is:
 1. A method of preparing a doped Si surface,comprising: a) cleaning a Si surface to remove oxides; and b) contactingthe cleaned Si surface with a dilute dopant solution comprisingtetraethylene glycol dimethyl ether (tetraglyme) and a dopant materialeffective for doping a Si surface, wherein said contacting is for a timeand at a temperature effective to form a layer of dopant material on thesurface, and wherein said dopant comprises material from Group III ofthe Periodic Table, Group V of the Periodic Table or a combinationthereof.
 2. The method of claim 1 wherein the dopant comprises arsenicor gallium.
 3. The method of claim 1 wherein the method further includesthe step of applying a capping layer to the doped area.
 4. The method ofclaim 3 wherein the method further includes the step of diffusing thedopant into the Si surface by annealing the treated Si substrate.
 5. Themethod of claim 1 wherein said dilute dopant solution comprises anadditional solvent in addition to tetraethylene glycol dimethyl ether.6. A method of doping a Si surface, comprising: a) cleaning a Si surfaceto remove oxides; b) contacting the cleaned Si surface with a dilutedopant solution comprising tetraethylene glycol dimethyl ether(tetraglyme) and a dopant material effective for doping a Si surface,and c) applying a capping layer to the doped area; and d) diffusing thedopant into the Si surface by annealing the treated Si substrate,wherein said contacting is for a time and at a temperature effective toform a layer of dopant material on the surface, and wherein said dopantcomprises material from Group III of the Periodic Table, Group V of thePeriodic Table or a combination thereof.
 7. The method of claim 6wherein the method additionally includes the step of treating thecleaned Si surface with 3-methyl-3-methoxybutanol prior to contactingwith the dilute dopant solution.
 8. The method of claim 6 wherein saiddopant material is provided in an amount of between 1% and 20%.
 9. Themethod of claim 6 wherein said dopant material is provided in an amountof 4% or less.
 10. The method of claim 6 wherein said dopant comprisesarsenic or gallium.
 11. A method of preparing a doped Si surface,comprising: a) cleaning a Si surface to remove oxides; and b) contactingthe cleaned Si surface with a dilute dopant solution comprising: i) atleast one solvent selected from the group consisting of tetraethyleneglycol dimethyl ether, triethylene glycol dimethyl ether, diethyleneglycol dimethyl ether, dimethylsulfoxide, dimethylsulfone,N-methylpyrrolidone, 1 formyl piperidine, Isopar M, ethanolamine,diethanolamine, triethanolamine, linoleic acid, oleic acid, palmitoleicacid, safflower oil, grape seed oil, poppyseed oil, sunflower oil, hempoil, corn oil, wheat germ oil, cottonseed oil, soybean oil, walnut oil,sesame oil, rice bran oil, pistachio oil, peanut oil, canola oil,chicken fat, egg yolk, linseed oil, lard, olive oil, palm oil, cocoabutter, macadamia oil, butter, and coconut oil; and ii) a dopantmaterial comprising material from Group III of the Periodic Table, GroupV of the Periodic Table or a combination thereof, wherein saidcontacting is for a time and at a temperature effective to form a layerof dopant material on the surface.
 12. The method according to claim 11,wherein the dopant comprises arsenic or gallium.
 13. The method of claim11 wherein the method further includes the step of applying a cappinglayer to the doped area.
 14. The method of claim 13 wherein the methodfurther includes the step of diffusing the dopant into the Si surface byannealing the treated Si substrate.
 15. The method of claim 11 whereinthe method additionally includes the step of treating the cleaned Sisurface with 3-methyl-3-methoxybutanol prior to contacting with thedilute dopant solution.
 16. The method of claim 11 wherein said solventis tetraethylene glycol dimethyl ether.
 17. The method of claim 11wherein said solvent includes tetraethylene glycol dimethyl ether and asecondary solvent selected from the group consisting of triethyleneglycol dimethyl ether, diethylene glycol dimethyl ether,dimethylsulfoxide, dimethylsulfone, N-methylpyrrolidone, 1 formylpiperidine, Isopar M, ethanolamine, diethanolamine, triethanolamine,linoleic acid, oleic acid, palmitoleic acid, safflower oil, grape seedoil, poppyseed oil, sunflower oil, hemp oil, corn oil, wheat germ oil,cottonseed oil, soybean oil, walnut oil, sesame oil, rice bran oil,pistachio oil, peanut oil, canola oil, chicken fat, egg yolk, linseedoil, lard, olive oil, palm oil, cocoa butter, macadamia oil, butter, andcoconut oil.
 18. The method of claim 11 wherein said dopant material isprovided in an amount of between 1% and 20%.
 19. The method of claim 11wherein said dopant material is provided in an amount of 4% or less.